JP3753181B2 - Gas analysis method - Google Patents

Description

  The present invention relates to a gas analysis method, and more specifically, a gas analysis method and a sample using a standard gas generation device having a standard gas generation device and a gas sample introduction device for introducing a standard gas produced by the standard gas generation device. The present invention relates to a mixed gas analysis method, a linearity determination method, and a repeatability determination method.

  In order to perform quantitative analysis using a gas chromatograph, it is necessary to calibrate in advance with a standard gas having a known concentration. This standard gas is usually produced by a manufacturer and is usually packed in a cylinder, and the time required for production may take several days to several weeks. In order to quantitatively analyze multicomponents over a wide range of concentrations, it is necessary to prepare a large number of standard gases in advance.

  The conventional diluter measures the pressure of the buffer tank into which the sample is introduced, and determines the concentration of the component from the partial pressure (dilution ratio). For this reason, the partial pressure of the buffer tank has to be adjusted to obtain a predetermined concentration, and the adjustment method is performed by controlling the amount of sample flowing into the buffer tank. However, in order to repeatedly reproduce the predetermined concentration only by controlling the inflow amount, it must be introduced into the buffer tank over an extremely small amount of time.

  When a gas sample is analyzed using a gas chromatograph, there are a method of introducing the collected gas sample into the gas chromatograph with a gas tight syringe and a method of introducing it with a measuring tube installed in the gas chromatograph introduction part. .

  When a gas tight syringe is used, since it is all manual work, a dedicated analyst is required, and in order to analyze a large number of samples continuously, the work is all night.

  Furthermore, a method using a measuring tube is generally used for a process gas chromatograph, and is used to continuously analyze a gas sample in a fixed line. In order to introduce a gas sample from the line to the measuring tube, the sample itself must be under pressure, and for accurate measurement, the line up to the measuring tube must be sufficiently purged with the sample, A large amount of sample is required.

The present invention has been proposed in view of various requirements in the case of analyzing a gas sample using the gas chromatograph described above, and analyzes any gas sample in any pressure state (pressurized, atmospheric pressure, negative pressure). A gas analysis method using a gas sample introduction device capable of being introduced into a means and capable of analyzing a large number of gas samples continuously and fully automatically, and a standard gas generator capable of easily producing a standard gas according to the gas sample to be measured, An object of the present invention is to provide a sample mixed gas analysis method, a linearity determination method, and a repeatability determination method.

  The gas analysis method of the present invention determines a gas sample introduction pressure in a gas analysis method using a gas analyzer having a standard gas generator and a gas sample introduction device for introducing a standard gas produced by the standard gas generator. Compare and confirm the reproducibility of the results obtained by repeatedly analyzing the same sample, the introducing pressure determining step, the introducing step of introducing the gas sample into the analysis means, the gas analyzing step of analyzing the introduced gas sample, It includes a comparison process, an alarm process for issuing an alarm if the comparison result is abnormal, and a data storage process for storing the analysis result, and each of these processes is performed fully automatically.

  Here, the gas sample introduction device used in the introduction step is provided with a plurality of containers filled with either gas or liquid with pipes each provided with a selection valve and a flow rate regulator in parallel. A switching valve that switches the connection of a plurality of pipes by providing a main pipe that communicates with each of the pipes, providing a plurality of buffer tanks (particularly preferably, a plurality of buffer tanks equipped with pressure gauges) in series. The switching valve is connected to each of a pipe communicating with the buffer tank, the other end of the main pipe, a pipe communicating with the analyzer, and a pipe communicating with the measuring pipe, and switches the connection of these pipes. It is preferable that a plurality of valves for opening and closing a pipe line made of the pipe and a vacuum pump for sucking a gas in the pipe line are provided.

  Next, the mixed gas analyzing method of the present invention uses a gas analyzer having a standard gas generator and a gas sample introducing device for introducing a standard gas produced by the standard gas generator, and using the sample mixed gas as a gas sample. Introducing and determining the introduction pressure of the gas sample, the introduction step of introducing the gas sample into the analysis means, the gas analysis step of analyzing the introduced gas sample, and repeatedly analyzing the same sample Including a comparison process that compares and confirms the reproducibility of the results obtained, an alarm process that issues an alarm if the comparison result is abnormal, and a data storage process that stores the analysis results. The gas analysis is performed, and the component of the sample mixed gas is determined using the analysis result of the standard gas.

  Here, the gas sample introduction device used in the introduction step is provided with a plurality of containers filled with either gas or liquid with pipes each provided with a selection valve and a flow rate regulator in parallel. A switching valve that switches the connection of a plurality of pipes by providing a main pipe that communicates with each of the pipes, providing a plurality of buffer tanks (particularly preferably, a plurality of buffer tanks equipped with pressure gauges) in series. The switching valve is connected to each of a pipe communicating with the buffer tank, the other end of the main pipe, a pipe communicating with the analyzer, and a pipe communicating with the measuring pipe, and switches the connection of these pipes. It is preferable that a plurality of valves for opening and closing a pipe line made of the pipe and a vacuum pump for sucking a gas in the pipe line are provided.

  The linearity determination method of the gas analyzer of the present invention includes a standard gas generator and a sample introduction pressure and an analysis result of a gas analyzer including a gas sample introduction device for introducing a standard gas produced by the standard gas generator. In the linearity determination method for determining linearity, a pressure selection step for selecting an introduction pressure of a gas sample, an introduction step for introducing the gas sample into the analysis means, a gas analysis step for analyzing the introduced gas sample, and analysis And a linearity determining step for determining the linearity of the result.

  In this linearity determination method, the gas sample introduction device used in the introduction step is parallel to a plurality of containers filled with either gas or liquid, each with a selection valve and a flow rate regulator. Provide a main pipe that is connected to each of these pipes and integrated into one pipe, and a plurality of buffer tanks (particularly preferably, a plurality of buffer tanks equipped with pressure gauges) are provided in series to connect a plurality of pipes. The switching valve is connected to each of a pipe communicating with the buffer tank, the other end of the main pipe, a pipe communicating with the analyzer, and a pipe communicating with the measuring pipe. It is preferable to provide a plurality of valves for opening and closing the pipe made of the pipe and a vacuum pump for sucking gas in the pipe.

  Furthermore, the repeatability determination method of the present invention for determining the repeatability of the analysis result of the gas analysis method has a standard gas generator and a gas sample introduction device for introducing a standard gas produced by the standard gas generator. In a repeatability determination method for determining repeatability of analysis results of a gas analysis method performed using a gas analyzer, a repeat count setting step for setting a repeat count and an introduction pressure determination for determining a gas sample introduction pressure A process, an introduction step of introducing a gas sample into the analysis means, a gas analysis step of analyzing the introduced gas sample, a comparison step of comparing and confirming the reproducibility of the analysis result, and an alarm if the comparison result is abnormal An alarm process to be issued, and a data storage process to store the analysis result.

  In this iterative reproducibility determination method, the gas sample introduction device used in the introduction process is arranged in parallel with a plurality of containers filled with either gas or liquid, each with a selection valve and a flow regulator. A plurality of buffer tanks (particularly preferably, a plurality of buffer tanks equipped with pressure gauges) are provided in series, and communicated with each of the pipes. A switching valve for switching the connection is provided, and the switching valve is connected to each of a pipe communicating with the buffer tank, the other end of the main pipe, a pipe communicating with the analyzer, and a pipe communicating with the measuring pipe. It is configured to switch the connection of the pipe, and it is preferable to provide a plurality of valves for opening and closing the pipe line composed of the pipe and a vacuum pump for sucking the gas in the pipe line. Arbitrariness.

  Alternatively, the gas analyzer has a standard gas generator and a gas sample introduction device, and the standard gas generator has a selection valve and a flow rate adjustment respectively in a plurality of containers filled with either gas or liquid. Piping with a vessel is provided in parallel, and each of these pipes communicates with one end of one main pipe, and the other end of the main pipe is equipped with a plurality of buffer tanks (particularly preferably equipped with pressure gauges). A plurality of buffer tanks) connected in series, branched from the main pipe and provided with pipes connected to the sample collection port and the dilution gas insertion port, and a plurality of valves for switching by opening and closing the pipes composed of these pipes And a vacuum pump for sucking the gas in the pipe line, and the gas sample introduction device includes a selection valve and a flow regulator respectively in a plurality of containers filled with either gas or liquid Intervening A plurality of buffer tanks (particularly preferably, a plurality of buffer tanks equipped with pressure gauges) are provided in series, and are connected in parallel to each other. A switching valve for switching the connection of a plurality of pipes is provided, and the switching valve is connected to each of a pipe communicating with the buffer tank, the other end of the main pipe, a pipe communicating with the analyzer, and a pipe communicating with the measuring pipe. The connection of these pipes is switched, and a plurality of valves for opening and closing the pipe line composed of the pipes and a vacuum pump for sucking the gas in the pipe line are provided. preferable.

  The gas analyzer used in the present invention is preferably a gas chromatograph. A plurality of analyzers may be provided. Moreover, it is preferable that the analysis method of the present invention is automatically controlled by a sequencer, and data processing, process management and report creation are performed by a personal computer.

  Since the present invention is configured as described above, various standard gases are produced by a built-in diluter according to the gas sample to be measured, and the gas is in any pressure state (pressurized, atmospheric pressure, negative pressure). Even a sample can be introduced into a gas chromatograph at a set pressure desired by an analyst, and the gas chromatograph can be calibrated, so that the sample can be accurately analyzed. A sample in any pressure state can be fully automatically introduced into the gas chromatograph. Therefore, gas analysis, sample mixed gas analysis, linearity determination, and repeatability determination can be performed automatically and accurately and efficiently.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 shows a flow path system of a gas diluter D for producing a standard gas according to the present invention. The normally closed valves b1 to b16 for selection are provided from cylinders filled with a sample gas (not shown), a mixed standard gas, and a plurality of pure gases (liquids) (total of 16 in this example). Pipings a1 to a16 connected to the flow rate regulators c1 to c16, respectively, and further provided with normally closed valves d1 to d16, respectively, are provided in parallel. The book is collected into a book and connected to the first buffer tank B1 via the normally closed valve V1.

  The first buffer tank B1 is connected to the second buffer tank B2 via the valve V3, and further connected to the first vacuum pump VP1 via the valve V4. A pipe L2 branches from between the valve V1 of the main pipe L and the first buffer tank B1 and is connected to the sample sampling port S via the valve V2, and a pipe into which dilution gas is introduced. L1 is connected from the valve f through the flow rate regulator g and the valve h.

  The first and second buffer tanks B1 and B2 are disposed in the thermostatic chamber CB. For example, the capacity of the first B1 is 200 to 400 milliliters (ml), and the second B2 is B2. About 400 to 600 milliliters (ml) is suitable. Valves, flow regulators, pipes, and the like are also heated to prevent sample liquefaction. On the other hand, the piping from the valves b1 to b16 and the flow rate regulators c1 to c16 of the pipings a1 to a16 are combined into one through the valves e1 to e16 and connected to the second vacuum pump VP2. .

  Here, reference numerals j1 and j2 denote valves for opening and closing the bypasses of the first and second vacuum pumps VP1 and VP2. Reference numerals P1 to P3 indicate pressure gauges. In other words, the first and second buffer tanks B1 and B2 are equipped with pressure gauges P1, P2, and P3.

  Next, a method for producing a standard gas using the gas diluter D for producing a standard gas according to the present invention will be described with reference to FIGS. In the figure, the black valve indicates a closed state.

First, when the partial pressure is high (for example, 200 mmHg or more), only the buffer tank B1 is used.
(A1) As shown in FIG. 2, the pure gas line to be diluted (a1, L in the illustrated example) is purged with the dilution gas introduced from the pipe L1 (line cleaning first step). In this case, it introduce | transduces by the negative pressure in a buffer tank, and pressurization of the gas for dilution.
(A2) Next, the line is evacuated by the vacuum pumps VP1 and VP2, and it is confirmed that the pressure is 0 mmHg by the pressure gauges P1, P2 and P3.
(A3) Then, if necessary, the pure gas line to be diluted is purged with the pure gas, and the sample is lined up.
(A5) When filling the sample, if the partial pressure is high, as shown in FIG. 3, the valve V3 is closed and only the buffer tank B1 is used. In the illustrated example, the sample gas is filled up to a predetermined pressure from the pipe a1. (Sample filling step).
(A6) Next, the valve V1 is closed and the pressure gauges P1 and P2 before and after the buffer tank B1 are kept stable until the pressure becomes equal, and the pressure is equalized. Pressure process). At this time, the fluctuation of the pressure value per unit time is checked, and if the fluctuation range falls within a predetermined tolerance, it is assumed that “pressure equalization” has been performed.
(A7) Next, as shown in FIG. 4, the dilution gas is filled up to a predetermined pressure (dilution gas filling step).
(A8) Then, the pressure gauges P1 and P2 before and after the buffer tank B1 are kept stable until they have the same value, and the pressure is equalized, and the pressure value is recorded (dilution gas equalization step).
(A9) Thus, as shown in FIG. 5, the standard gas is sampled from the standard gas sampling port S to the bag, cylinder or analyzer (standard gas sampling step).
(A10) After gas sampling, all the used lines are evacuated by the vacuum pumps VP1 and VP2, and the standard gas is eliminated (line cleaning process).

On the other hand, when the partial pressure is small, two buffer tanks B1 and B2 are used in the steps from the above (A5) sample filling step to (A9) standard gas sampling step.
(A5 ′) In the sample filling step, as shown in FIG. 6, the valve V3 is opened and the sample is filled to a predetermined pressure using both the buffer tanks B1 and B2.
(A6 ′) Then, in the pressure equalization step of the sample, pressure equalization is achieved using pressure gauges P1, P2, and P3.
(A7 ′) In the dilution gas filling step, as shown in FIG. 7, the dilution gas is filled into both buffer tanks B1 and B2 to a predetermined pressure.
(A8 ′) In the step of equalizing the dilution gas, the pressure is equalized using pressure gauges P1, P2, and P3.
(A9 ′) In the standard gas sampling step, as shown in FIG. 8, the standard gas is sampled from the standard gas sampling port S to the bag, cylinder or analyzer through the two tanks B1 and B2.

  As described above, according to the gas diluter D for standard gas production of the present invention, a plurality of buffer tanks B1 and B2 are connected in series, and when a predetermined partial pressure is high, one buffer tank B1 is When the partial pressure is low, by using two buffer tanks B1 and B2, a predetermined partial pressure can be obtained even if the introduction flow rate of the sample is very small. Since various pure gases are connected in parallel, standard gases of various components can be produced.

  FIG. 9 shows a flow path system of the gas sample introduction device T of the present invention. The pipes a1 to a16 to which the gas (liquid) cylinders on the left side of the figure are connected are the same as in the above embodiment. These pipes a1 to a16 are combined into one main pipe LA and communicated with one port of the switching valve V2A (configured as a six-way valve) via the valve V1. Further, the other port of the switching valve V2A is connected to the first buffer tank B1, and is connected to the second buffer tank B2 via the valve V3 and further to the first vacuum pump VP1 via the valve V4. It is communicated. Further, the other port of the switching valve V2A is connected to a pipe L2A into which the carrier gas is introduced, a pipe for introducing the sample gas into the gas analyzer (gas chromatograph) A, and a pipe connected to the measuring pipe MT. Normally, these communicate with the buffer tank B1 from the main pipe LA through the measuring pipe MT (the measuring pipe MT is located upstream of the buffer tank B1), and the pipe L2A into which the carrier gas is introduced is connected to the gas analyzer. It is arranged so as to communicate with A.

  The first and second buffer tanks B1 and B2, the measuring pipe MT, and the switching valve V2A are disposed in the thermostatic chamber CB. Valves, flow regulators, piping, and the like are also heated to prevent sample liquefaction.

  On the other hand, a pipe L1A to which a cleaning gas is supplied is communicated with a concentrated portion of the pipes a1 to a16 via a valve i.

Next, a method for introducing a gas sample into the gas analyzer using the gas sample introducing device T of the present invention will be described with reference to FIGS.
(B1) First, as shown in FIG. 10, a gas sample line to be measured (in the example shown, from the valve b1 of the pipe a1 to the valve V4 after the buffer tank B2 of the pipe LA) has the same kind as the carrier gas of the gas chromatograph. A cleaning gas is introduced from the pipe L1A and purged (first line cleaning step).
(B2) Then, the lines are evacuated by the vacuum pumps VP1 and VP2, and it is confirmed by the pressure gauges P1, P2 and P3 that the pressure is 0 mmHg (second line cleaning step). In addition, more effective line cleaning can be performed by repeating the first and second cleaning steps.
(B3) Next, the gas sample line to be measured is purged with the sample gas (the first step which may be a line with the sample).
(B4) Then, the line is evacuated by the vacuum pumps VP1 and VP2, and it is confirmed that the pressure is 0 mmHg by the pressure gauges P1, P2 and P3 (the second step which may be a line by the sample). If both the first and second steps are repeated, impurities in the line can be removed more effectively. Note that the first and second steps may be omitted.
(B5) Next, as shown in FIG. 11, the measuring tube MT and the buffer tank B1 are filled with sample gas (sample filling step).
(B6) Then, the pressure gauges P1 and P2 before and after the switching valve V2A and the buffer tank B1 are stabilized and kept at the same value to equalize the pressure (sample pressure equalization step). The “equal pressure equalization” is the same as described in the step (A6).
(B7) Next, as shown in FIG. 12, the switching valve V2A is switched to introduce the sample gas into the gas chromatograph (introduction step of the sample into the gas analyzer).
(B8) After the measurement, the measured gas sample line is evacuated to remove the sample gas (line cleaning step).

When the pressure of the sample gas introduced into the gas analyzer A1 is low, two buffer tanks B1 and B2 are used. That is,
(B5 ′) In the sample filling step, as shown in FIG. 17, the measuring tube MT and the buffer tanks B1 and B2 are filled with the sample.
(B6 ′) Further, in the pressure equalization step of the sample, the pressure gauges P1, P2, and P3 are allowed to stand until the pressure gauges P1, P2, and P3 become stable and have the same value, thereby equalizing the pressure.
Since (B1)-(B4), (B7), and (B8) are the same, redundant description is omitted.

  Thus, according to the gas sample introduction device T of the present invention, the buffer tanks B1 and B2 are provided downstream of the measuring pipe MT. Conventionally, since the measuring tube is small (0.5 to 2 ml) (0.5-2 ml), it is impossible to set the introducing pressure because the pressure state of the sample to be introduced is not constant with only the measuring tube. However, according to the method of the present invention, a gas sample in any pressure state (pressurized, atmospheric pressure, negative pressure) can be introduced into the gas chromatograph at a set pressure desired by the analyst. For example, even a small amount of gas sample of 100 milliliters (ml) or less can be introduced into the gas analyzer A.

  Next, the configuration of the gas analyzer A used in the present invention will be described. A gas chromatograph is generally used for the analysis means G1 shown in FIG. An analysis result storage means G2 for storing data of the analysis result of the analysis means G1 and a comparison means G3 for comparing and determining the reproducibility of the data are provided, and the number of comparisons is counted within a predetermined number of times. For example, a comparison number counter G5 that feeds back to the analysis means G1 and outputs a message to the alarm means G6 that outputs a message if the analysis result is abnormal is provided, and data storage for storing the introduced gas data, analysis result data, etc. Means G4 is provided.

  FIG. 15 shows a flowchart of a standard gas (pure gas) analysis method. First, the standard gas value is input (step S1), and the introduction pressure is determined (step S2, introduction pressure determination step). And the standard gas manufactured with the standard gas generator D is introduce | transduced into the analysis means G1 via the gas sample introduction apparatus T (step S3, introduction process). Next, it is determined whether or not the introduction pressure is within an allowable range (step S4). If No, the process returns to step S3. If Yes, gas analysis is performed (step S5, gas analysis step). And the result is memorize | stored in the analysis result memory | storage means G2, and the continuous reproducibility is confirmed twice by the comparison means G3 (step S6, comparison process). If it is No, it is counted by the comparison number counter G5, and it is determined whether or not it is within a predetermined number of times (step S8). If Yes, the process returns to Step S3 and the analysis is repeated. If No, a message is output by the alarm means G6 (Step S9, alarm process), and the process ends. If step S6 is Yes, the data storage means G4 stores the introduction pressure and the data of the peak area of the gas chromatograph (step S7, data storage step), and the process ends.

  FIG. 16 shows the configuration of a gas analyzer for analyzing a mixed gas. In addition to the configuration described with reference to FIG. 14, there is further provided a sum calculation means G7 for calculating the component of the sample gas from the data storage means G4 and calculating the sum of the raw data, and the sum calculation means G7 allows the sum to be allowed. There are provided second alarm means G6A for outputting a message when the range is exceeded, normalizing means G8 for normalizing the result of the sum calculating means G7, and a printer display G9 for printing out the result.

  FIG. 17 shows a flowchart of a method for analyzing a mixed gas having the configuration shown in FIG. First, the mixed gas value is input (step S1A), and the introduction pressure is determined (step S2, introduction pressure determination step). Then, the mixed gas is introduced into the analysis means G1 via the gas sample introduction device T (step S3A, introduction step), and it is determined whether or not the introduction pressure is within an allowable range (step S4). If it is No, it will return to step S1A, and if it is Yes, gas analysis will be performed (step S5, gas analysis process). And the result is memorize | stored in the analysis result memory | storage means G2, and the continuous reproducibility is confirmed twice by the comparison means G3 (step S6, comparison process). If No, it is counted by the comparison number counter G5, and it is determined whether or not it is within a predetermined number (step S8). If Yes, the process returns to Step S3A and the analysis is repeated. If No, a message is output from the alarm means G6 (Step S9, alarm process), and the process ends. If YES in step S6, the data storage means G4 stores the introduction pressure of each component and the peak area data of the gas chromatograph (step S7A, data storage process), and the component calculation means G7 stores the standard gas analysis result. The component is calculated from (Step S10). Next, the total calculation means G8 determines whether the total sum of the raw data is 100% ± 1%. If No, the second alarm means G6A outputs a message (step S14) and the process is terminated. If Yes, the normalizing means G9 normalizes the sum to 100% (step S12), prints the analysis result on the printer display G10 (step S13), and ends.

  FIG. 18 shows a configuration used for determining the linearity of the sample introduction pressure and the analysis result of the gas analyzer. That is, it comprises pressure selection means G11, analysis means G1, data storage means G4, printer display G10 that outputs the result, and alarm means G6 that outputs a message.

  FIG. 19 shows a flowchart of a method for determining the linearity of the sample introduction pressure of the gas analyzer and the analysis result. First, the pressure selection means G11 selects the gas type to be introduced into the analysis means G1 (step S21, pressure selection step), and determines the introduction pressure (step S22). Then, the selected gas is introduced into the analysis means G1 through the gas sample introduction device T (step S23, introduction step), and it is determined whether the introduction pressure is within the range (step S24). If No, the process returns to step S21. If Yes, gas analysis is performed (step S25, gas analysis process), and the data storage means G4 stores the introduction pressure and the data of the peak area of the gas chromatograph (step S26). Data storage process). Then, it is determined whether or not the introduction pressure variable (for example, 100 to 700 mmHg) determined in Step S22 has ended (Step S27). If No, the process returns to Step S22 and analysis is performed at the next introduction pressure. If the variable is terminated and step S27 is Yes, the printer display G10 displays a graph and prints out (step S28). From the result, linearity is determined (step S29, linearity determination step). If Yes, the process ends. If No, a message is output by the alarm means G6 (step S30, alarm process), and the process ends.

  FIG. 20 and FIG. 21 show a configuration used for determining the reproducibility of the analysis result. FIG. 20 shows a configuration for determining the reproducibility of the analysis of the standard gas, provided with a repetition number setting means G12, and the subsequent configuration is the same as the configuration described in FIG. FIG. 21 shows a configuration for determining the reproducibility of the analysis of the mixed gas. Similarly, the repetition number setting means G12 is provided, and the subsequent configuration is the same as the configuration described in FIG.

  FIG. 22 shows a flowchart of a method for determining the repeatability of analysis results. First, in the repetition number setting means G12, the gas type, the gas concentration, and the number of repetitions for determining reproducibility are input (step S41, repetition number setting step), and the introduction pressure is determined (step S42, introduction pressure determination step). . Then, the measurement gas is introduced into the analysis means G1 via the standard gas generator D (in the case of the standard gas) and the gas sample introduction device T (step S43, introduction process), and it is determined whether the introduction pressure is within the range (step). S44). If it is No, it will return to step S43, and if it is Yes, a gas analysis will be performed (step S45, gas analysis process), and it memorize | stores in the analysis result memory | storage means G2. Then, the comparison means G3 determines whether or not the number of repetitions is within a predetermined number (step S46). If Yes, the comparison is counted by the comparison number counter G5 and returns to step S43. A message is output by the alarm means G6. If No, the data storage means G4 stores the data of the introduction pressure and the peak area of the gas chromatograph (step S47, data storage process), prints out each data, standard deviation, etc. (step S48) and ends. .

The figure which shows the flow-path system of the gas diluter for standard gas manufacture of this invention. The flow-path system figure which shows the line washing | cleaning 1st process of FIG. FIG. 2 is a flow path system diagram illustrating a filling process of the sample in FIG. 1. FIG. 2 is a flow path system diagram showing a dilution gas filling step of FIG. 1. The flow-path system figure which shows the extraction process of the standard gas of FIG. The flow-path system diagram which shows the filling process of the sample when partial pressure is low. FIG. 7 is a flow path system diagram showing a dilution gas filling step of FIG. 6. FIG. 7 is a flow path system diagram showing the standard gas sampling step of FIG. 6. The figure which shows the flow-path type | system | group of the gas sample introduction apparatus of this invention. The flow-path system figure which shows the line washing | cleaning 1st process of FIG. FIG. 10 is a flow path system diagram illustrating a filling process of the sample of FIG. 9. The flow-path system | strain diagram which shows the introduction process to the gas chromatograph of the sample of FIG. FIG. 10 is a flow path system diagram illustrating a filling process of the sample of FIG. 9. The block diagram which shows the structure of the analyzer of this invention. The flowchart figure of the analysis of standard gas. The block diagram which shows the structure of mixed gas analysis. The flowchart figure of the analysis of mixed gas. The block diagram which shows the structure of the linearity determination of an analyzer. The flowchart figure of the linearity determination of an analyzer. The block diagram which shows the structure of the reproducibility determination of the analysis of standard gas. The block diagram which shows the structure of the reproducibility determination of the analysis of mixed gas. The flowchart figure of repeated reproducibility determination.

Explanation of symbols

A ... Gas analyzer B1, B2 ... Buffer tank D ... Diluter MT ... Metering tube L, L1, L2, L1A, L2A ... Piping P1-P3 ... Pressure gauge S ..Sample sampling port T ... Gas sample introduction device V1-V4, V2A ... Valve VP1, VP2 ... Vacuum pump a1-a16 ... Piping b1-b16 ... Valve c1-c16 ... Flow regulators d1 to d16 ... Valve e1 to e16 ... Valve f ... Valve g ... Flow regulators h, i, j1, j2 ... Valve

Claims (4)

In a gas analysis method using a standard gas generator and a gas analyzer having a gas sample introduction device for introducing a standard gas produced by the standard gas generator, an introduction pressure determination step for determining an introduction pressure of the gas sample, and a gas The introduction process of introducing the sample into the analysis means, the gas analysis process of analyzing the introduced gas sample, the comparison process of comparing and confirming the reproducibility of the results obtained by repeatedly analyzing the same sample, and the comparison result is abnormal If so, a gas analysis method comprising an alarm process for issuing an alarm and a data storage process for storing an analysis result, and each of these processes is performed fully automatically. An introduction pressure for introducing a sample gas mixture as a gas sample and determining an introduction pressure of the gas sample using a gas analyzer having a standard gas generator and a gas sample introduction device for introducing a standard gas produced by the standard gas generator. A determination step, an introduction step of introducing a gas sample into the analysis means, a gas analysis step of analyzing the introduced gas sample, and a comparison step of comparing and confirming the reproducibility of the results obtained by repeatedly analyzing the same sample , Including an alarm process for issuing an alarm if the comparison result is abnormal, and a data storage process for storing the analysis result, and performing these processes fully automatically to perform the gas analysis, and to obtain the analysis result of the standard gas A method for analyzing a sample mixed gas, comprising: determining a component of the sample mixed gas. Introduction of gas sample in linearity determination method for determining linearity of sample introduction pressure and analysis result of gas analyzer including standard gas generator and gas sample introduction device for introducing standard gas produced by this standard gas generator A pressure selection step for selecting pressure, an introduction step for introducing a gas sample into the analysis means, a gas analysis step for analyzing the introduced gas sample, and a linearity determination step for determining linearity of the analysis result A method for determining linearity of a gas analyzer characterized by the following. Repetitive reproducibility judgment for judging repetitive reproducibility of analysis results of a gas analysis method performed using a gas analyzer having a standard gas generator and a gas sample introduction device for introducing a standard gas produced by the standard gas generator In the method, a repetition number setting step for setting the number of repetitions, an introduction pressure determination step for determining the introduction pressure of the gas sample, an introduction step for introducing the gas sample into the analysis means, and a gas analysis for analyzing the introduced gas sample Repetitive reproducibility characterized in that it includes a process, a comparison process for comparing and confirming the reproducibility of the analysis result, an alarm process for issuing an alarm if the comparison result is abnormal, and a data storage process for storing the analysis result Judgment method.

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